Water-insoluble azo dyestuffs



(AN=NB) -(W '1H-OH,-s0,z) n (I) In the above formula A and B denotearomatic-carbocyclic or heterocyclic radicals, W denotes a radical R1 NN CH50, -(OCHgCHg -O or --COO,-CH CH O-, and Z stands for an alkylradical containing 1 to 3 carbon atoms. If W stands for a radical otherthan N/Ri R2 the radicals R and Z may also be linked with one anotherwith the formation of a heterocyclic radical of the formula R denotes adirect linkage or an alkylene radical containing l to Zcarbon atoms. Rdenotes. hydrogen, alkyl or acyl, whereby the alkyl or acyl radical mayalso be a constituent of a heterocyclic ring together with the nitrogenatom; R, R R and R denote hydrogen or alkyl radicals; m, n stand forWhole numbers from 1 to 3 and n stands for a whole number of-O.-s3,preferably 0-1.

The new dyestuffs are to be free from sulfonic acid and carboxylic acidgroups, but may otherwise contain any substituents usually present inazo dyestuifs such as cyan, halogen, alkyl, nitro, alkoxy, cyanalkyl,hydroxalkyl, acyloxyalkyl, alkoxyalkyl, hydroxyalkoxyalkyl and sulphonegroups. According to definition, alkyl radicals also include isoalkylradicals.

The watereinsoluble dyestuffs according to the present invention areproduced by coupling aromatic-carbocyclic or heterocyclic diazocompounds corresponding to the radical A with azo componentscorresponding to the radical B, and choosing the components in such amanner that the final dyestuffs contain 1 to 3 groupings of the formulait (II) wherein W, R and Z have the aforesaid significance, but

do not'contain any water-solubilizing, acid-dissociating groups.

For this purpose, for example, starting components are chosen whichalready contain the grouping (II). Components which meet this conditionmay be produced, for example, by condensing in diazo or couplingcomponents, preferably in the presence of acid-binding agents, agrouping NH-R with a haloalkylsulphone United States Patent 6 3,177,198Patented Apr. 6, 1965 wherein R has the above significance and haLrepresents a reactive halogen atom, or by, adding an alkylvinyl sulphoneby means of an aci rcatalysis, thus obtaining components with thegrouping /Rt N,

(fiH-GHg-SOrZ R It is also possible to react a grouping.

Groupings of the aforesaid type wherein the radicals R and Z are linkedwith one another with the formation of a hetero ring R4--CHR6.

GE: S a

may be introduced into the starting components or into azo dyestuffsthemselves, by reacting, for example according to the process of GermanPatent No. 682,079, in these present groups with butadiene sulphone(-thiophendihydro 1,l-dioxide) or its 3,4-alkyl-substitutipn products.By this method there may be prepared inter alia the following startingcomponents which are used as diazo or coupling components for theproduction of the new azo dyestuffs:

CH1 /CH3- S 7 ame 0 CHrCHz-0CH-CH1 CH1 7 H:

4;. Diazo and coupling components containing the groupings are obtainedby addition of vinylalkyl sulphones or their substitution products tothe groupings CH2OH,I

+ alkylvinyl sulfone) and which are also listed below:

(infant-0N GHPCHF-W-CHQCHI s 0 -021 6 yields on terephthalic acid esterfibres, when dyed in conventional manner with the addition of dispersingand swelling agents, a clear ruby red. shade of very good fastnessproperties.

The azo component used is prepared in the following H CHg-CHg-O-CHgCHgS0202115 5 manner:

A mixture of 45.3 parts of N-methyl-N-fl-hydroxyethyl aniline and 1 partof sodium methylate is heated to 60 C. and then slowly treated with 36parts of vinylethyl sulphone. The reaction mixture is subsequently 1stirred at 50-70 C. for 3-5 hours and then. added with stirring to about200 parts of Water. The aqueous phase CH3 CHF-CHi-OCHICH2SOtOaH1 isseparated after neutralisation and the residual viscous portion heatedto 140-150 C. in a vacuum for the re- This process also may be appliedto the previously moval of the unreacted oxethylated-amine. 63 parts ofsynthesized azo dyestuifs provided the latter possess the a yellow oilare obtained having the constitution above mentioned OH group-containingsubstituents. CH3

The dyestuffs according to the invention are eminently suitable for thedyeing of terephthalic acid ester fibres, polyamide fibres, polyvinylfibres and cellulose ester OHH OHT O CHEOHZ-S02-02116 fibres. Thedyeings on terephthalic acid ester fibres are Analysis: S calculated11.83%, found 11.85%.

In Table lfurther valuable dyestuffs are listed which are obtainable bya suitable replacement of the diazo component used in Example 1. Thedyestuffs are characterized by the shade of the dyeing on terephthalicacid very fast to sublimation and wettreatrnent, and are generally alsovery fastto light. Since the dyestuffs are insoluble or sparinglysoluble in. water, the dyeing process is advantageously carried out inthe presence of dispersmg agents; in order to accelerate the dyeingprocess, ester fibres.

Table 1 Example Diazo component Azo component Shade 2 '4-thiocyano-1aminobenzene As Example 1 Yellow. 3 4-amino-benzaldehyde do Orange.2,4-dl0hl01'm1ilino do Yellow.

Z-amino-benzthimole dn Red.

2-amino-5-methyl-1,3,4-thiodiazole do Orange.2-amino5-thiocyano-4-methyldo Bordeaux.

thiazole-(LES). 2,4-dicyananiline- Red. 3phenyl-B-arnino-thiodiazole(1,2,4) Scarlet. 2-chloro-4 nitraniline Red. 1 l2.6-(lichl0lo-4-nifraniline Orange-brown. 123,5-diehloro-4-amino-benzene sul Yellow.

phonamide.

' EXAMPLE 13 swellingagents may also be added to the dyebath, ifdesired.

In the following examples which are given for the purpose ofillustrating the invention, the parts are parts by weight if nototherwise indicated.

EXAMPLE 1 2.5 parts of 2-cyano-4-nitranilineare dissolved in 25 parts ofconcentrated sulphuric acid and diazotised at 0 C. for 30 minutes with4.6 parts of nitrosyl-sulphuric acid. After pouring the solution intoice water and freeing it from insoluble impurities by filtration, it isadded to a solution of 3.93 parts of the addition product of N-precipitates and is isolated by suction filtration.methyl-N-hydroxyethyl-aniline to vinylethyl sulphone in The dyestufiyields on terephthalic acid ester fibres, dilute hydrochloric acid.Coupling sets in immediately dyed at C. in a closed vessel with theaddition of and iscompleted by buffering. The dyestuif thus obtaineddispersing agents, an intense reddish brown shade of very and having theconstitution good fastness properties.

8. precipitates and is isolated by. suction filtration- The dyestuti.yields on .terephthalic acid ester fibres an'intense violet shade; a

In Table 4 further valuable dyestuffs are listed which In Table 2further valuable dyestui fs are listed which are obtainable by suitablereplacement of the diazo component used in Example 9. The dyestuffsarecharacterized by the shade of the dyeing on terephthalic acid esterfibres. are obtainable by suitable replacement of the diazo com- Table 2Example Dlazo component I Azo component Shade 2-cyano-4-m'tranlline AsExample 13 Violet; 3,5.dichloro-4-aminobenzene-sulphonic -do Orange.

acid amide. 2-chlom4-nitraniline -do Redlzordeaux. l-amino-2-methoxy-4-nltrobenzone do Red. 1-amino-3-chloro6-benzene-carboxyllc doOrange.

acid amide. 1-amino-3-chloro-6-cyanobenzene do Do.3-phenyl-5-amino-thiodiazole- (1,2,4) do Red. 2-amino-fi-nitrothiazole-(1,3) do Blue. 4 nitro-2-methyl-1-aminobenzene do Red.2,4-dicyananiline. Do. l-amino-Z,5-dimethoxy-4-eyanobendo Orange.

zene.

EXAMPLE 3.5 parts of the addition productof 2-aminobenzyl alcohol tovinyl ethyl sulphone are dissolved in 5 parts ponent used in Example 29.The dyestutlsare characterized by the shade of the dyeingronterephthalic acid ester fibres.

Table 4 Diazo component Azo component Shade 2,4-dicyananiline As Example29---- Ruby-red. 2-ch1oro4-nitraniline .do Bordeaux.2,fi-diChIOlO-l-nlfmnlline Brown.

3-phenyl-5-amino-thiodiazole-(1,2,4) Red. 3-ethlylmercapto-aaminothiodiazolc- D0.

of concentratedhydrochloric acid and 50 parts of water,

and diazotised ,With'l part of sodium'nitrite dissolved in 10 parts ofwater. This solution is then added to a solution of 6.1 parts of theaddition product of 1 mol of N,N-

in dilute hydrochloric acid. Upon buffering the solution, couplingstarts immediately. The dyestuff formed which possesses the constitutionCHf-CHg-O-CHg-OHz-S02-02 5 V H 0-CH;GHg-SOaz s is isolated by suctionfiltration.

In .Table 3 further dyestuffs are listed which may be obtained bysuitable replacement of the diazo component used in Example 25. Thedyestuffs are characterized by the shade of the dyeing on polyamidefibres.

.dihydroxyethylaniline to 2 mol of vinylethyl-sulphone.

Example 35 parts of the addition product-of 4-arnino-benzyl alcohol tovinylethyl sulphone are dissolved in a mixture of 5 parts ofconcentrated hydrochloric acid and 50 parts of water, diazotised with 1part of sodium nitrite dissolved in Water, and coupled soda-alkalinewith 2.55 parts of 1-phenyl-S-methyl-pyrazolone. The yellow dyestuifwhich possesses the constitution precipitates and is; isolated bysuction filtration. When dyed on cellulose esterfibres, the dyestuifyields a clear EXAMPLE 29 2.5 parts of 2-cyano-4-nitraniline arediazotised as described in Example 1. The solution of the diazonium saltis then added to a solution of 2.3 parts of the addition product of1N-acetyl-N-methyl-N-hydroxyethyl-1,3- phenylenediamine to vinylmethylsulphone in dilute hydrochloric acid. Coupling starts. immediately andis greenish yellow shade of very good fastness to Wet processing andfood fastness to light.

- Example 36 2.5 parts of 2-cyano-4-nitraniline aredissolved in25 partsof concentrated sulphuric acid and diazotised at completed by bulfering.The dyestuif which possesses 0 C. for 30 minutes'with 4.6 parts ofnitrosylsulphuric the constitution /CH3 N N NHOO CH acid. When thesolution has been poured into ice water and liberated by filtration fromthe insoluble impurities, it is added to a solution of 3.9 parts of theaddition product of N-methyl-N-hydroxyethyl aniline to butadienesulphonein dilute hydrochloricacid. The coupling which startsimmediatelyis completed by bulfering. The dye- In Table 5 further valuabledyestuffs are listed which are obtainable by suitable replacement of thediazo com: ponent used in Example 36. The dyestuffs are characterized bythe shade of the dyeing on terephthalic acid 5 ester fibres.

stuff thus obtained which possesses the constitution 3 parts of2,6-dichloro-4-nitraniline are dissolved in 15 parts of sulphuric acidof 60 Baum and then diazotised at about 40 C. for minutes with 4.6 partsof nitrosylsulphuric acid. After stirring the solution into ice waterand liberating it by filtration from insoluble impurities, it is addedto a solution of 4.3 parts of'the addition product ofN-ethyl-N-hydroxyethyl-m-toluidine E to butadiene sulphone in dilutehydrochloric acid. Cou- 301 pling starts immediately and 'is completedby buffering.

30 The dyestutf formed which possesses the constitution yieldsonterephthalic acid ester fibres, dyed in conventional manner with theaddition of dispersing agents, a clear ruby red shade of very goodfastness Properties.

The azo component used is prepared in the following manner: 1 t 1 Amixture of 75 parts of N-methyl-N-B-hydroxyethylaniline and 0.8 part ofsodium methylate is heated to 30 C. and then slowly treated with 60parts of butadiene sulphone. After a short fall of temperature, thetemperature then slowly rises to about 50 0., care being taken that thistemperature. is not exceeded. The reaction mixture is subsequentlystirred at 30-40 C. for a further 3-5 hours and then added with stirringto about 200 parts of water. The aqueousphase containing unre actedbutadiene: sulphone is separated and the residual viscous portion heatedto 140-150 C..in a vacuum in order CgHs precipitates and is isolated bysuction filtration.

On terephthalic acid ester fibres the dyestufi yields, up-

on addition of dispersing agents at 120 C. in a closed vessel, anintense reddish brown shade of very good fastness properties.

In Table 6 further valuable dyestufis are listed which are obtainable bysuitable replacement of the. diazo ester fibres.

Table. 6

Example Diazo component Azo component Shade 2-cyano-4-nitraniline AsExample 44-- Violet. 3,5-d10hlOr0-4aminobenzenesulphonic --do Orange.

acid amide. 2-ehl )ro-4-n.itraniline Bordeaux.l-amrno-Zanethoxy-tnitro-benzene. e1-am1no-3-chloro-fi-benzene-carboxylic Orange.

acld amide. 1-ammo-3-ohloro-fi-oyano-benzene 0- 3-phenyl-5-amino-thiodiazole-(l,2 4) Red. 2-am1no-5-nitro-thiazole-(1,3) 14-nttro-2-methyl-l-amin obenzene Red. 2,4-d1cyananiline Do.Lamino-Z,5-dimethoxy-4-cyano- Orange.

benzene.

to remove the unreacted oxethylated amine. of a yellow oil of theconstitution 127.5 parts are obtained.

Analysis: Ncalculated 5.2%, found 5.22%; S calculated 11.9%, found11.6%.

EXAMPLE 56 3.5 parts of the addition product of Z-aminobenzyl alcohol tobutadiene sulphone are dissolved in 5 parts of concentrated hydrochloricacid and 50 parts of water and diazotised with 1 part of sodium nitritedissolved in 10 ti coupling starts immediately. possesses theconstitution The dyestufi formed which t2; ish yellow shade of very goodfastness 'to-wetprocessing and good fastness to light.

EXAMPLE 67 S01 fi 2.5 parts of 2-cyano-4-nitraniline are diazotisedasdea 5. scribed in Example'36. The solution of the diazonium /OHPOHPOCHCHZ salt is then added to a solutionof 3.9 parts of the addi- N=N.--Nvtion product of N,N-dimethy1-2-amino-benzyl alcohol to butadienesulphonein dilute hydrochloric acid. Coupling JH OCHCHn CH2 CH2 Hz startsimmediately and is completed by bufiering. The

If dyestuff formed which possesses the constitution 1 SO oat-0E2 a CH5CE: is isolated by suction filtration.v

In Table 7 further dyestuffs are listed which may be obtained bysuitable replacement of the diazo component Nwm), used in Example 55.The dyestuifs are characterized by the shade of the dyeing on polyamide.fibres.

Table 7 Example Diazo component Azo component Shade 572-eyano-4-nirmnflino I As Example 56.". Violet. 582-ehloro'4-nitranili11e do- Red-bordeaux. 595-amino-3-phenyl-thiodiazole-(1,2,4) do Ruby red.

EXAMPLE 60 2.5 parts of 2-cyano-4-nitraniline are diazotised' asdescribed in Example 36. The solution of the diazonium salt is thenadded to a solution of 2.4 parts of the addition product of 1N-acetyl-N'-methyl-N-hydroxyethyl1,3-phenylene-diamine to butadienesulphone in dilute hydrochloric acid. Coupling starts immediately and iscompleted by buffering. The .dyestuff which possesses the constitutionong-em-o-orn-on,

N NHOO CH3 7 I Table 8 dyes terephthalic acid ester fibres in bluish'redshades which are very fast towet-treatmentand sublimation.

EXAMPLE 68 4.2 parts of sodium nitrite are dissolved at a maximumtemperature of 70 C. in 30 parts by volume of concentrated sulphuricacid, cooled to 10 C. and diluted with 60 parts by volume ofglacial-acetic acid. Into this mixture there are added at 10 C. inportions 9.9 parts of 4- m'tro-Z-cyananiline, subsequently dilutedwitha' further 60 parts by volume of glacial acetic acid and stirred at 10C. for ,1-2 hours. The mixture is then poured onto 350 parts ofice, theexcess nitrous acid removed and the clear diazo solution combined with ahydrochloric acid solution of 13.7 parts, ofN-ethyl-N-(methylsulphonylethyl)-aniline. The ice-cold mixture isneutralised with a sodium-hydroxide solution to a pH of 4, coupling thustaking place. The dyestufi precipitated in a powdery form and having theformula is filtered olf with suction, washed with Water and dried.

Example Diazo component Azo component Shade 2,4-dicyananiline2-ehloro-4-nitraniliue L;

Ruby red. Bordeaux. Brown- Red.

EXAMPLE 66 so, 7 N i precipitates andisisolated ,by suction filtration.Dyed on cellulose ester fibres, the dyestuff yields a clear green- Itdyes from'an aqueousdispersion polyethylene-terephthalate and celluloseester fibres in strong, intense bluish red shades of very good fastnessto wet treatment, sublimation and'light.

N-ethyl-N-(methylsulphonylethyl)-aniline used as coupling component maybe obtained, for example, as follows: Into v125 parts of N-ethyl-anilinethere are added dropwise in an oil bath heated to 120 C. with stirringand passing over nitrogen within about /2 hours parts ofmethyl-(fl-chlorethyl)-sulphone. The internal temperature is maintainedat about 135 C. due, to the reaction heat. The mixture is subsequentlystirred at 100 C. for a further 6 hours and after, cooling stirred for 12 hours with 100 parts by volume of benzene and 23 parts of calcinedsoda. After termination of the CO evolution the precipitated common saltis filtered off, the henzene distilled olf from the filtrate and theresidue fractionated by distillation in a high vacuum: first runnings 68parts of ethyl aniline (B.P. 57 C./0.1 mm. Hg), main fraction, B.P.184-l85 C./0.1 mm. Hg, 92 parts of N- ethyl N(methylsulphonylethyl)-aniline (a pale yellow oil solidifying incrystalline form).

EXAMPLE 69 ume of water. After buffer-ingwith ice cooling withsodiurnacetate and a sodium hydroxide solution to a pH valeu of 4, couplingoccurs; The precipitated powdery dyestufi is filtered off with suction;washed'with water and dried. It dyes from an aqueous dispersionpolyester fibres in. strong, intense. reddish brown shades of very goodfastness to wettreatment, sublimation and light.

N-ethyl-N-(methylsulphonylethyl)-rn-toluidine .used as couplingcomponent may be obtained according to the instructions given in Example68, paragraph 2 when instead of 125 parts of N-ethylaniline;v 140 partsof N-ethylm-toluidine are reacted with parts ofmethyl-B-chlorethyl-sulphone. The product goes over at 171 C./ 0.05

mm. Hgas a viscous, pale-yellowish liquid which solidifies incrystalline form after. a short. time.

The dyeulfs described in. the following. table. are produced.accordingtothe data given. in the preceding examples by coupling. ofthe corresponding diazotised amines with the appropriatecouplingcomponentsg Shade of dyeing of fabric of- Exarnple Diazo-componentCoupling-component Cellulose- Polyethylene Polyamlde acetateterephthalate CH2CH2 'S02CH3 a 4-aminobenzoic-acid methyl R1= CH ReddishReddlsh Reddish ester. n= yellow yellow. yellow.4-aminobenzene-sulphonic acid- R1= CH do Do.

dimethylamide. 6= 2-arnino-4-nitro-benzoic acid R1=CH3 Reddish do methylester. R =H yellow. 2,4-dlcyananiline R =CHa Reddish Reddish R6 orange.orange. 74 4-nitr iline Rl=OZH5 Reddish R =H orange 752-chloro-4-nitraniline R1=OH Yellowish Reddish Bluish red.

R =H red. yellow 76 2,4-dicyananillne Ri=IOIzH Orange Orange.

77 2-chloro-4-nitraniline R1=H2CHZOH Yellawish Yellgwlsh 6= re re 78-2-cyano-4-nltranillne 1=OH2OH2OH Bluish red... Bluish red- 793-nltraniline R1=CH2CH2OH Reddish Reddish Reddish RFH yellow. yellow.yellow. 80 2,4-dlcy mniline R1=CHzCH2OH Orange 6= Zamino-Mritro-benzoicacid R CHQCHQOH Reddish Reddish methyl ester. a=H yellow. yellow4-aminoazobenzene R1=CH2CH1OH Yellowish Orange Reddish Ru= orange.orange. 4-nitraniline R1=C2H5 Reddish Reddish Yellowish R5 OH; orange.orange. orange. 2-nminobenzthlazole R1=C2H5 Scarlet Yellowis luish R=CH3 scarlet scarlet. 3-nitranlline R1=C2H5 Reddish Reddlsh ReddlshRa=CHa yellow. yellow yellow. 2,4-dicyanoaniline R1=C2H5 ReddishYellowish Scarlet.

R CHa orange. scarlet 3-phenyl-5-amlno-thiodiazole-l, R1=G2H5 Blulshred- Bluish red 2,4. Ra= CH3 2,4-dinltranillne R|=C2H5 Ruby BlulshRa=CHs bordeaux. 2-methoxy-4mitranlline R1=C2H5 Yellowish Bluish red.

Rd 0H3 red. 2-cyano-4-nitraniline Ri=CHzCHi-OOC-CHz Bluish red" Bluishred... Reddlsh bordeaux. 2,6-diehl0rO-4-nltranillne CHzCHg-SOz-CH;Orange Orange Brick red.

O brown. brown.

92 2-cyano-4-nitraniline /CH2CHzOCH2CHr-SO2CH3 Bluish red- Bluish red.

CHzGHzoCH2CH2SOrCH3 We claim: 1. v A dyestuffof the formula wherein B'isa component of the benzene series, R is C H and n is an integer of 0-1;when n is 0, R isrH,

Z is lower ;alkyl, and A is a component having the formula wherein P isa member selected from the group consiste ing of hydrogen and chlorine,andQ is a member selected from'the group consisting of chlorine andcyano; and

when n is 1, R is a member'selected-from the group consisting ofhydrogen and lower alkyl, 2 is lower alkyl of 1-3 carbon atoms, R is Hand R 'and Z,-incombina-, tion, form a ring having the general formula-CHCH;

and A is a member selected from the class consisting of a component ofthe benzene, thiazole and thiodiazole series; the dyestuif acid groups;

2. The dyestufi of the formula I a s being'free of sulfonic acid andcarboxylic- 3. Thedyestufi of theforrnula oaHs 4. The dyestuir" of-theformula J Grimm-scram 5 The dyestuifof the formula 7. The dyestutf ofthe formula I CgHs References Cited in the file of this patent UNITEDSTATES PATENTS 7 2,830,043 Mer-ian Apr. 8, 1958 2,955,901 Km'ckenbe-rgOct. 11, 1960

1. A DYESTUFF OF THE FORMULA